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      Recent Progress in Ferrocene-Modified Thin Films and Nanoparticles for Biosensors

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          Abstract

          This article reviews recent progress in the development of ferrocene (Fc)-modified thin films and nanoparticles in relation to their biosensor applications. Redox-active materials in enzyme biosensors commonly use Fc derivatives, which mediate electron transfer between the electrode and enzyme active site. Either voltammetric or amperometric signals originating from redox reactions of Fc are detected or modulated by the binding of analytes on the electrode. Fc-modified thin films have been prepared by a variety of protocols, including in situ polymerization, layer-by-layer (LbL) deposition, host-guest complexation and molecular recognitions. In situ polymerization provides a facile way to form Fc thin films, because the Fc polymers are directly deposited onto the electrode surface. LbL deposition, which can modulate the film thickness and Fc content, is suitable for preparing well-organized thin films. Other techniques, such as host-guest complexation and protein-based molecular recognition, are useful for preparing Fc thin films. Fc-modified Au nanoparticles have been widely used as redox-active materials to fabricate electrochemical biosensors. Fc derivatives are often attached to Au nanoparticles through a thiol-Au linkage. Nanoparticles consisting of inorganic porous materials, such as zeolites and iron oxide, and nanoparticle-based composite materials have also been used to prepare Fc-modified nanoparticles. To construct biosensors, Fc-modified nanoparticles are immobilized on the electrode surface together with enzymes.

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          Layer-by-layer assembly as a versatile bottom-up nanofabrication technique for exploratory research and realistic application.

          The layer-by-layer (LbL) adsorption technique offers an easy and inexpensive process for multilayer formation and allows a variety of materials to be incorporated within the film structures. Therefore, the LbL assembly method can be regarded as a versatile bottom-up nanofabrication technique. Research fields concerned with LbL assembly have developed rapidly but some important physicochemical aspects remain uninvestigated. In this review, we will introduce several examples from physicochemical investigations regarding the basics of this method to advanced research aimed at practical applications. These are selected mostly from recent reports and should stimulate many physical chemists and chemical physicists in the further development of LbL assembly. In order to further understand the mechanism of the LbL assembly process, theoretical work, including thermodynamics calculations, has been conducted. Additionally, the use of molecular dynamics simulation has been proposed. Recently, many kinds of physicochemical molecular interactions, including hydrogen bonding, charge transfer interactions, and stereo-complex formation, have been used. The combination of the LbL method with other fabrication techniques such as spin-coating, spraying, and photolithography has also been extensively researched. These improvements have enabled preparation of LbL films composed of various materials contained in well-designed nanostructures. The resulting structures can be used to investigate basic physicochemical phenomena where relative distances between interacting groups is of great importance. Similarly, LbL structures prepared by such advanced techniques are used widely for development of functional systems for physical applications from photovoltaic devices and field effect transistors to biochemical applications including nano-sized reactors and drug delivery systems.
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            Polyelectrolyte complexes: bulk phases and colloidal systems.

            When aqueous solutions of polycations and polyanions are mixed, polyelectrolyte complexes form. These are usually insoluble in water, so that they separate out as a new concentrated polymer phase, called a complex coacervate. The behavior of these complexes is reviewed, with emphasis on new measurements that shed light on their structural and mechanical properties, such as cohesive energy, interfacial tension, and viscoelasticity. It turns out that stoichiometric complexes can be considered in many respects as pseudo-neutral, weakly hydrophobic polymers, which are insoluble in water, but become progressively more soluble as salt is added. In fact, the solubility-enhancing effect of salt is quite analogous to that of temperature for polymers in apolar solvents. Since two-phase systems can be prepared in colloidal form, we also discuss several kinds of colloids or 'microphases' that can arise due to polyelectrolyte complexation, such as thin films, 'zipper' brushes, micelles, and micellar networks. A characteristic feature of these charge-driven two-phase systems is that two polymeric ingredients are needed, but that some deviation from strict stoichiometry is tolerated. This turns out to nicely explain how and when the layer-by-layer method works, how a 'leverage rule' applies to the density of the 'zipper brush', and why soluble complexes or micelles appear in a certain window of composition. As variations on the theme, we discuss micelles with metal ions in the core, due to incorporation of supramolecular coordination polyelectrolytes, and micellar networks, which form a new kind of physical gels with unusual properties. Copyright © 2011 Elsevier Inc. All rights reserved.
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              A Critical Review of Glucose Biosensors Based on Carbon Nanomaterials: Carbon Nanotubes and Graphene

              There has been an explosion of research into the physical and chemical properties of carbon-based nanomaterials, since the discovery of carbon nanotubes (CNTs) by Iijima in 1991. Carbon nanomaterials offer unique advantages in several areas, like high surface-volume ratio, high electrical conductivity, chemical stability and strong mechanical strength, and are thus frequently being incorporated into sensing elements. Carbon nanomaterial-based sensors generally have higher sensitivities and a lower detection limit than conventional ones. In this review, a brief history of glucose biosensors is firstly presented. The carbon nanotube and grapheme-based biosensors, are introduced in Sections 3 and 4, respectively, which cover synthesis methods, up-to-date sensing approaches and nonenzymatic hybrid sensors. Finally, we briefly outline the current status and future direction for carbon nanomaterials to be used in the sensing area.
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                Author and article information

                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                06 December 2013
                December 2013
                : 6
                : 12
                : 5742-5762
                Affiliations
                Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan; E-Mail: t-shigehiro@ 123456m.tohoku.ac.jp
                Author notes
                [* ]Author to whom correspondence should be addressed; E-Mail: junanzai@ 123456mail.pharm.tohoku.ac.jp ; Tel.: +81-22-795-6841; Fax: +81-22-795-6840.
                Article
                materials-06-05742
                10.3390/ma6125742
                5452732
                af80cc63-436f-4c55-866f-8fa81119b09f
                © 2013 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution license ( http://creativecommons.org/licenses/by/3.0/).

                History
                : 30 October 2013
                : 02 December 2013
                : 02 December 2013
                Categories
                Review

                ferrocene,biosensor,electron-transfer mediator,thin film,electro-polymerization,layer-by-layer deposition,au nanoparticle

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